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CN1947274A - Electroluminescent polymers containing planar arylamine units, the preparation and use thereof - Google Patents

Electroluminescent polymers containing planar arylamine units, the preparation and use thereof Download PDF

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Publication number
CN1947274A
CN1947274A CNA2005800132033A CN200580013203A CN1947274A CN 1947274 A CN1947274 A CN 1947274A CN A2005800132033 A CNA2005800132033 A CN A2005800132033A CN 200580013203 A CN200580013203 A CN 200580013203A CN 1947274 A CN1947274 A CN 1947274A
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阿米尔·帕勒姆
苏珊·霍伊恩
奥雷莉·法尔库
阿尔内·比辛
潘君友
海因里希·贝克尔
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Merck Patent GmbH
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Abstract

The invention relates to polymers, comprising certain triarylamine units of formula (I). Said materials have a greater lifespan than conventional materials and are thus more suited for use in polymeric organic light diodes.

Description

The electroluminescent polymer that comprises planar arylamine units, its preparation and purposes
Carried out about 13 years about display and the business-like broad research of illumination component based on polymerization (organic) light-emitting diode (PLEDs).This development starts from disclosed basic research in WO 90/13148.Though can obtain simple recently on the market but first product (small displays on the PHILIPS N.V. razor).Yet, still need the significant improvement of institute's materials used, so that these displays become the real competitor of the LCD (LCDs) in present dominant force market.
For producing three kinds of all glow colors, be necessary specific comonomer copolymerization is gone in the corresponding polymer (referring to, for example, WO 00/46321, WO 03/020790 and WO 02/077060). hereinFrom the coloured light base polymer that turns blue (" main chain "), can produce other two kinds of primary colors then usually, red and green.
Reported in addition and inserted the improvement that specific fragrant amino group can produce character:
WO 99/54385 has described poly-fluorenes, and its efficient and working voltage can be by with triphenylamines, tetraphenyl-p-phenylenediamine (PPD), perhaps tetraphenyl-4,4 '-the derivative copolymerization of benzidine base goes into the corresponding polymer main chain and improves.
WO 01/49769 has described the polymer that comprises three fragrant amino groups, and wherein at least one aromatic yl group is a heteroaryl.The special advantage of these polymer is not described.
WO 04/037887 has described and has comprised the substituent three arylamine unit of fused-aryl, such as the naphthyl unit.These are particularly suitable for the application of passive drive.
WO 04/106409 described in conjugated polymer three-and four three arylamine as hole conductor and luminous element.
WO 05/017065 proposes to replace triarylamine derivative as hole conductor by the triaryl phosphine derivative in conjugated polymer.
According to prior art, some polymer have demonstrated good performance when being used for PLEDs.Though obtained progress, yet they also do not have to satisfy the requirement that is used for high quality applications.Particularly, green, the life-span of the polymer of the coloured light that especially turns blue is still not enough for many application.
Now unexpectedly find, comprise two (three arylamine) conjugation of unit or the partly conjugated polymer of specific plane, have the extraordinary performance that is better than prior art.These particularly relate to the polymer life-span, and the current/voltage curve and the efficient of polymer.Thereby, the present invention relates to these polymer and its purposes in PLEDs.
Tetraphenyl-p-phenylenediamine (PPD) that its center cell (phenylene) has planar structure equally causes strong colour shift and is not suitable for this purpose because it combines meeting with some monomers.
US 6066712 has described and has replaced, by the divinyl arylene units with by group that condense, ring-type more, and the hole injection of polymer of forming such as the aromatic diamine of fluorenes or the luxuriant and rich with fragrance bridge joint of dihydro.As if yet these polymer are not suitable for the application of high-quality OLED, because when they are used for OLEDs, at 1mA/cm only 2Extremely low current density (therefore extremely low brightness) realization down is about the life-span of the non-constant of (in the order of) 200h.
The present invention relates to comprise at least O.1mol%, preferred 1mol% at least, especially preferred 5mol% at least, preferred especially especially conjugation of the general formula of 7mol% (1) unit at least or partly conjugated polymer,
General formula (1)
Wherein, the described symbol of use and mark have following implication:
A is in occurring each time, and is identical or different, is N, P or As;
X is in occurring each time, and identical or different, for having the divalence planar conjugate system of 6-40 carbon atom, it comprises 2 arlydene at least, and can be by R 1Replace;
Ar 1, Ar 2, Ar 3, Ar 4, Ar 5Identical or different in occurring each time, be fragrance or heteroaromatic ring system with 2-40 carbon atom, they can be by one or more R 1Group replaces, and condition is if this group does not have the straight key that combines with polymer chain, Ar 1-Ar 5Group is not all represented the condensed ring system;
R 1Identical or different in occurring each time, be H, F, Cl, Br, I, CN, NO 2, OH, N (R 1) 2, Si (R 2) 3, B (R 2) 2, have the straight chain of 1-40 carbon atom, side chain or cycloalkyl, alkoxyl or thio alkoxy, wherein, in addition, one or more non-adjacent carbon atoms can be by-CR 2=CR 2-,-C ≡ C-,-NR 2-,-O-,-S-,-CO-O-or-O-CO-O-replaces, wherein, in addition, one or more H atoms can be replaced by fluorine, have the aryl of 2-40 carbon atom, heteroaryl, aryloxy group or heteroaryloxy, wherein, in addition, one or more carbon atoms can be by O, S or N replace, and in addition can be by one or more non-aromatic radicals R 1Replace; Two or more herein R 1Group also can form aliphatic series or aromatic series each other, monocycle or polycyclic system;
R 2Identical or different in occurring each time, be H or aliphatic series or aromatic hydrocarbon group with 1-20 carbon atom;
N is identical or different in occurring each time, is 0,1 or 2;
The unit and the polymer of general formula (1) pass through Ar 1-Ar 5One or two of the unit connects;
Except the polymer of general formula (2),
Figure A20058001320300091
General formula (2)
Wherein: Ar 21, Ar 22, Ar 24Each arlydene naturally, it can the carrier band substituting group; Ar 25Be arlydene or many fused rings of divalence group, it can the carrier band substituting group; Ar 23And Ar 26Each alkyl naturally, aralkyl, perhaps aryl, it can the carrier band substituting group; m 1Be 0,1,2 or 3; n 1It is natural number.
Polymer of the present invention is conjugation preferably.
The unit of general formula (1) can be incorporated in the main chain or side chain of polymer, preferably enters into main chain.If the unit of general formula (1) is combined into the main chain of polymer, then Ar 1-Ar 5Two of group is the divalent group that is connected on the polymer chain, and other is univalent perssad.If the combination of the unit of general formula (1) enters in the side chain of polymer, then group Ar 1-Ar 5One be the divalent group that is connected with polymer chain, and other is univalent perssad.
Although apparent from describe, should spell out once more herein, the construction unit of general formula (1) can be asymmetric replacement, promptly different atom A, different radicals X and/or different group Ar 1-Ar 5Perhaps different substituent R 1And R 2May reside in the unit, perhaps these also can be combined in different positions.
For purpose of the present invention, " conjugated system on divalence plane " is described as symbol X, be meant finger comprise at least two each other and with the divalence conjugated system of the arlydene of atom A conjugation, its dihedral angle is less than 35 °, preferably less than 30 °, especially preferably less than 25 °.Because dihedral angle that measure or that calculate always depends on assay method, should determine by quantum chemistry calculation so be used for the dihedral angle of the object of the invention.For this purpose, by means of " Berny " optimization (H.B.Schlegel et al., J.Comp.Chem.1996,17,49) use semi-empirical approach AM1 (M.J.S.Dewar et al. for example, J.Am.Chem.Soc.1985,107,3902) in internal coordinate, determine geometric shape.Pass through the density function theory then, and use mixed function B3PW91 (J.P.Perdew, Phys.Rev.B 1996,54,16533) and " division valency layer " basis function group (" split valence " base set) 6-31G (d) (J.A.Pople et al., J.Phys.Chem.1971,54,724) calculating energy and track, Gaussian 98 program packages (J.A.Pople, Gaussian, Inc. are used in all calculating, Pittsburgh PA, 2001) carry out.
The conjugated system on plane described herein needn't only comprise the conjugation group, but also can comprise for example fatty bridge of bridge joint arlydene, therefore influences the flatness of system.Described system can be substituted equally, and wherein substituting group itself also can form one or more ring systems then.Preferably by do not depart from the rigid plane conjugated system of flatness around the singly-bound rotation.
The example of planar conjugate system is fluorenes (dihedral angle of diamines is 0.1 °), trans indenofluorene (dihedral angle of diamines is 0.5 °), dihydro phenanthrene (dihedral angle of diamines is 20.2 °) and tolans (dihedral angle of diamines is 0.7 °), wherein said tolans is not the rigidity system.On the contrary, the dihedral angle as the biphenyl that uses according to prior art is 42 °; Therefore biphenyl is not the system on plane.
Purpose for this application, arylene group is thought and is meant divalence fragrance or heteroaromatic group simple or that condense, such as phenylene, naphthylene or the like, and for example biphenyl system or fluorenes system do not mean and are meant simple arylene group, because two phenylene-units are herein by singly-bound combination (with in fluorenes, equally by other non-conjugated bridge combination).Aryl described here comprises 6 carbon atoms at least, and described heteroaromatic group comprises at least 2 carbon atoms.
For purpose of the present invention, fragrance or heteroaromatic ring system mean the system that needn't only comprise fragrance or heteroaromatic group that is meant, but wherein a plurality of fragrance or heteroaromatic group also can be by short non-fragrant unit (＜10% the atoms except H, atom=the interruption except H preferably＜5% is such as sp 3The C of-hydridization, O, N or the like.Therefore, for example 9,9 '-spiral shell two fluorenes, 9, the 9-diaryl fluorene, systems such as three arylamine mean equally for this goal of the invention and to be meant aromatic ring.Aromatic ring described here comprises 6 carbon atoms at least, and described heteroaromatic ring system comprises 2 carbon atoms at least.
For purpose of the present invention, C 1-C 40Alkyl, wherein, in addition, single H atom or CH 2Group can be replaced by the above-mentioned group mentioned, particularly preferredly is meant following group: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, the 2-methyl butyl, n-pentyl, sec-amyl, cyclopenta, n-hexyl, cyclohexyl, n-heptyl, suberyl, n-octyl, ring octyl group, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl group, 2,2, the 2-trifluoroethyl, vinyl, acrylic, cyclobutenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclo-octene base, acetenyl, propinyl, butynyl, pentynyl, hexin base or octyne base.C 1-C 40-alkoxyl especially preferably refers to methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy or 2-methyl butoxy.Fragrance or heteroaromatic ring system with 2-40 carbon atom, it also can be replaced by the above-mentioned radicals R mentioned under each situation, and can connect by the position of any hope of fastening at described fragrance or heteroaromatic rings, is meant particularly derived from the group of following compound: benzene, naphthalene, anthracene, phenanthrene, pyrene is bent Asia puecon, fluoranthene, four acenes, pentacene, BaP, biphenyl, biphenylene, terphenyl, three diphenylenes, fluorenes, spiral shell two fluorenes, the dihydro phenanthrene, dihydropyrene, tetrahydrochysene pyrene, cis or trans indenofluorene, furans, benzofuran, isobenzofuran, dibenzofurans, thiophene, benzothiophene, different benzothiophene, dibenzothiophenes, pyrroles, indoles, iso-indoles, carbazole, pyridine, quinoline, isoquinolin, acridine, phenanthridines, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenthazine ， phenoxazine, pyrazoles, indazole, imidazoles, benzimidazole, naphtho-imidazoles, phenanthro-imidazoles, pyridine-imidazole, pyrazine and imidazoles, quinoxaline and imidazoles ， oxazole, benzoxazole Nai Bing oxazole, En Bing oxazole, Fei Bing oxazole ， isoxazole, 1,2-thiazole, 1,3-thiazoles, benzothiazole, pyridazine, benzo pyridazine, pyrimidine, the benzo pyrimidine, quinoxaline, 1,5-phenazine, 2,7-phenodiazine pyrene, 2,3-phenodiazine pyrene, 1,6-phenodiazine pyrene, 1,8-phenodiazine pyrene, 4,5-phenodiazine pyrene, 4,5,9,10-four nitrogen Asia puecons, pyrazine, azophenlyene phenoxazine, phenthazine, fluorubin, naphthyridines, the azepine carbazole, benzo carboline, phenanthroline, 1,2,3-triazole, 1,2, the 4-triazole, BTA, 1,2, the 3-oxadiazole, 1,2, the 4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2, the 3-thiadiazoles, 1,2, the 4-thiadiazoles, 1,2,5-thiadiazoles, 1,3,4-thiadiazoles, 1,3, the 5-triazine, 1,2, the 4-triazine, 1,2,3-triazine, tetrazolium, 1,2,4, the 5-tetrazine, 1,2,3, the 4-tetrazine, 1,2,3, the 5-tetrazine, purine, pteridine, indolizine, and diazosulfide.
For the object of the invention, conjugated polymer is mainly to comprise sp on main chain 2The polymer of the carbon atom of-hydridization (perhaps also optional is sp-hydridization), described carbon atom also can be replaced by corresponding hetero-atom.Under the simplest situation, this is meant and alternately has two keys and singly-bound in described main chain.Main being meant causes natural (non-random) defective that conjugation is interrupted can not influence term " conjugated polymer ".If arylamine for example in addition, aryl phosphine or aryl arsenic unit, unit such as general formula (1), and/or specific heterocyclic group (promptly passes through N, O, P or S atom conjugation) and/or organometallic complex (promptly by the metallic atom conjugation) when being arranged in described main chain, this term conjugation also in the application's text, used.On the contrary, the unit is such as simple alkyl bridge, (sulfo-) ether, and ester, acid amides or imide bond will clearly be defined as non-conjugated segment.Partly conjugated polymer means and is meant wherein conjugation section long relatively in described main chain by non-conjugated intersegmental disconnected polymer, perhaps comprises the polymer of long relatively conjugation section in main chain is the side chain of non-conjugated polymer.
Can pass through fragrant unit Ar 1-Ar 5The position of any hope is incorporated into general formula (1) unit in the conjugated polymer.Preferably by group Ar 1Be incorporated into the side chain neutralization by group Ar 1And Ar 3Be incorporated in the main chain.Here preferably connect like this, it makes even carbon atom (perhaps corresponding hetero-atom, i.e. N, O and/or S) be positioned at described polymer and described nitrogen, perhaps between the connection of phosphorus or arsenic atom A.The quantity of carbon atom (perhaps corresponding hetero-atom) is preferably four multiple especially.
Except that the unit of general formula (1), polymer of the present invention equally preferably comprises other construction unit, and therefore should be called copolymer.Herein also can be with reference to a large amount of open and list of references of enumerating therein of particularly being correlated with in WO 02/077060 and among the WO 05/014689.These other construction units for example can be derived from classification as described below:
Class 1: the unit of representation polymer skeleton:
Such unit is to comprise those of aromatic carbon ring structure with 6-40 carbon atom, and it can be to replace or unsubstituted.Suitable herein is fluorene derivative (for example EP 0842208, and WO 99/54385, and WO 00/22027, and WO 00/22026, and WO 00/46321).In addition, spirobifluorene derivative (for example EP 0707020, and EP 0894107, and WO 03/020790) is possible equally.Equally proposed to comprise the combination of polymers (WO 02/077060) of two kinds of monomeric units of mentioning first.WO 05/014689 has described the dihydro phenanthrene derivative.In addition, cis or trans indenofluorene derivative (for example GB 0226010.7, and WO 04/113412) is suitable, and also has for example dihydropyrene or tetrahydrochysene pyrene derivatives and the other aromatic structure of clearly not listing.
Class 2: the unit of modifying form or glow color
Not only can influence form, and the construction unit that can influence the glow color that obtains polymer is possible equally.Here preferred the replacement or unsubstituted aromatic structure, perhaps be similarly tolans, stilbene or diphenylethyllene arylene derivatives with 6-40 carbon atom, such as 1,4-phenylene, 1, the 4-naphthylene, 1,4-or 9, the 10-anthrylene, 1,6-or 2,7-or 4, the inferior pyrenyl of 9-, 3,9-or 3, the inferior perylene of 10-, 2,7-or 3,6-phenanthrylene, 4,4 '-biphenylene, 4,4 " Ya triphenyl; 4,4 '-two-1,1 '-naphthylene; 4,4 '-Ya stilbene radicals or 4,4 " diphenylethyllene arylene derivatives.
Class 3: improve the hole injection of polymer and/or the unit of transmission characteristic
These are aromatic amine or electron rich heterocycle normally, such as replacing or unsubstituted triarylamine benzidine, N, N, N ', N '-four aryl p-phenylenediamine (PPD), triaryl phosphine, phenthazine ， phenoxazine, dihydrophenazine, thianthrene, dibenzo Dui bioxin, phenoxathiynes, carbazole, azulenes, thiophene, the pyrroles, furans and contain O in addition, the heterocycle of S or N with high HOMO (HOMO=is the highest to be occupied molecular orbit).Yet because the unit of general formula (1) has had hole conduction character, therefore polymer of the present invention also can have enough hole conductivities even without the other hole-transfer unit of other use.
Class 4: improve the electronics injection of polymer and/or the unit of transmission characteristic
These are sub-aromatic hydrocarbons of short of electricity or heterocycle normally, such as replacing or unsubstituted pyridine, pyrimidine, pyridazine, pyrazine oxadiazole, quinoline, quinoxaline, diazosulfide or azophenlyene, also can be following compound such as triarylborane and other O, the heterocycle of S or N of containing with low LUMO (LUMO=lowest unoccupied molecular orbital).
Class 5: unit with combination of class 3 and class 4 individual units
The structure that can preferably wherein improve hole mobility and raising electron mobility equally is present in according in the polymer of the present invention the unit of direct combination each other.Some made glow colors of these unit are changed into green, and are yellow or red; Therefore their purposes for example is suitable for producing from the polymer of the coloured light that turns blue at first other glow color.
Class 6: the luminous or unit of improvement from singlet to the triplet state transition from triplet state
The construction unit of class 6 is promptly to show those of electroluminescent phosphorescence rather than electroluminescent fluorescent from triplet state even high efficiency light-emitting at room temperature.What be suitable for this purpose at first is to comprise the compound of atomic number greater than 36 heavy atom.Particularly suitable compound comprises d or f transition metal, satisfies those of this condition.Especially especially preferably comprise 8-10 family element (Ru, Os, Rh, Ir, Pd, Pt), the construction unit of iridium and/or platinum particularly.These metal complexs can be in conjunction with entering described main polymer chain and/or side chain.
For using such construction unit, preferably use, thereby improve from singlet to the triplet state transition and improve the other construction unit of electroluminescent phosphorescence performance with mode of loading.What be suitable for this purpose for example is carbazole unit, and preferred bridge joint carbazole dimer unit described in WO 04/070772 and WO 04/113468, also can be ketone unit for example, described in undocumented application DE10349033.7.
Be preferably polymer of the present invention except that the construction unit of general formula (1), also comprise one or more unit that are selected from class 1-6 in addition.Here also advantageously, exist simultaneously from one of 1-6 class more than one construction unit.
Be preferably polymer especially except that general formula (1) unit, also comprise the unit of class 1, especially especially preferably comprise these unit of 50mol% at least.The unit of class 1 is preferably selected from spiral shell two fluorenes, fluorenes, and the dihydro phenanthrene, the indenofluorene of cis and/or trans indenofluorene are that it replaces or unsubstituted.
The ratio of the unit of preferred formula (1) is 1-50mol%.Special preferred proportion is general formula (1) unit of 5-30mol%, and especially special preferred proportion is 7-15mol%.Proved that this ratio is particularly suitable, especially for electroluminescent polymer.For other application, such as the charge transfer polymer in various application, obviously more a high proportion of general formula (1) unit may be fit to, for example up to the unit of the general formula (1) of 100mol%.
Preferred polymer of the present invention wherein A in occurring each time, identical or different, represent N or P, especially preferably N.Preferred in addition polymer of the present invention is symbol X wherein, and is identical or different, in occurring each time, represents the unit of general formula (3),
Figure A20058001320300161
General formula (3)
The wherein following sign flag of using that is suitable for:
Y is in occurring each time, and is identical or different, for-C (R 1) 2-,-C (R 1) 2-C (R 1) 2-,-N (R 1)-,-O-,-S-,-P (R 1)-,-P (=O) (R 1)-,-O-C (R 1) 2-or-O-C (=O)-, preferred-C (R 1) 2-or-C (R 1) 2-C (R 1) 2-;
M is in occurring each time, and identical or different is, and 0 or 1, preferred 0, wherein under the situation of symbol m=0, group Y omits, and does not correspond to chemical bond;
O, p are in occurring each time, and identical or different is, and 0 or 1, condition is that o and p can not be 0 simultaneously, wherein under one of mark o or p were 0 situation, group y was omitted, and does not correspond to chemical bond;
Q is in occurring each time, and identical or different is 0,1 or 2, preferred 0 or 1;
Dotted line key in the general formula (3) is represented being connected of atom A in the construction unit of this general formula and general formula (1) herein.
Preferred in addition polymer of the present invention is symbol Ar wherein 1-Ar 5, identical or different in occurring each time, representative have 4-30 carbon atom, can be by R 1The fragrance or the heteroaromatic ring system that replace, what preferably have a 6-25 carbon atom can be by R 1The fragrance or the heteroaromatic ring system that replace.
This symbol external n preferably represents 0 or 1, especially preferably represents 0.
The unit of the symmetry of preferred formula (1) in addition.This is preferably because the more easily synthetic accessibility of described monomer.Therefore, be preferably for all A in general formula (1) unit all identically, and preferred described unit has Ar 1-Ar 5Symmetrical structure.If there are a plurality of unit X, then these should to be preferably equally be identical.
The example of the unit of general formula (1) is the structure shown in embodiment (1)-(30), and dotted line key is wherein represented the connection in the polymer.For the purpose of clearer, do not provide possible substituting group usually, but for synthetic reason, solubility, the reason of efficient or system stability may be preferred.
Figure A20058001320300171
Polymer of the present invention or comprise the homopolymers of general formula (1) unit, or copolymer.Except that one or more structures of general formula (1), copolymer of the present invention may have other structures of one or more above-mentioned class 1-6 that mention.Copolymer of the present invention can have random, and structure that replace or block-wise perhaps can have a plurality of these structures of alternately arranging equally.The method that wherein can obtain to have the copolymer of block-wise structure is for example being described in detail among the WO 05/014688.These become the application's a part as a reference.Should emphasize also that in this described polymer need not have linear chain structure, and can be side chain for it also, perhaps also can have tree.
Polymer of the present invention preferably has 10-10, and 000, preferred especially 20-5000, preferred especially especially 50-2000 repetitive.
Polymer of the present invention passes through the polymerization preparation of the monomer of one or more types usually, and wherein at least a monomer produces general formula (1) unit in the described polymer.Many corresponding polymerization reactions are arranged in principle.Yet verified here, the several reaction types that cause C-C or C-N bonding are especially successful:
The SUZUKI polymerization;
The YAMAMOTO polymerization;
The STILLE polymerization;
The HARTWIG-BUCHWALD polymerization.
In for example WO 03/048225 or WO 04/022626, describe the method that to carry out polymerization by these methods in detail, with the method for separating described polymer from reaction medium and purifying.
The corresponding monomer of synthetic needs for polymer.Synthetic for from the unit of class 1-6 is referring to WO 05/014689 and the list of references quoted therein.
The monomer that causes the construction unit of the general formula (1) in the polymer of the present invention is corresponding triarylamine derivative (perhaps corresponding phosphorus and an arsenic derivative), it can suitably replace in position, and has and can make these monomeric units be introduced in suitable degree of functionality in the described polymer.
These monomers are novel, are theme of the present invention equally therefore.
The present invention relates to the bifunctional monomer compound of general formula (4) and general formula (5) in addition,
General formula (4) general formula (5)
A wherein, X, Ar 1, Ar 2, Ar 3, Ar 4, Ar 5, R 1, R 2Have and identical implication described in the general formula (1) with n, and in addition:
Z is in occurring each time, and is identical or different, but is the functional group of copolymerization under C-C or C-N bonding reaction condition, is preferably Cl, Br, I, O-tosylate, O-trifluoromethayl sulfonic acid ester, O-SO 2R 1, B (OR 1) 2Perhaps Sn (R 1) 3, be preferably Br especially, I, B (OR 1) 2Perhaps Sn (R 1) 3
R is 0 or 1.
The reaction of described C-C bonding is preferably selected from the SUZUKI coupling, YAMAMOTO coupling and STILLE coupling; Described C-N bonding reaction is preferably the HARTWIG-BUCHWALD coupling.
For functional monomer's compound of general formula (4) and general formula (5), be suitable for herein aforesaid with for the construction unit of general formula (1) identical preferably.
Be not preferably in addition polymer of the present invention is used as pure material, and replace conduct and other any polymerization of wishing type, oligomeric, material dendrite or low-molecular-weight uses as mixture (blend) together.These can for example improve Electronic Performance or own luminous.Yet, for example being the form of the film of control viscosity of solution or formation, the blend composition of electronics inertia also is suitable.Therefore the blend of this type also is a part of the present invention.
The present invention relates to one or more polymer of the present invention or blend solution and the preparation in one or more solvents in addition.For example at WO 02/072714, in WO 03/019694 and the document wherein quoted the method for preparing polymer solution has been described.For example by the method (for example spin coating) of surface-coated, perhaps printing process (for example ink jet printing) can be used for preparing thin polymeric layer to these solution.
Polymer of the present invention and blend can be used for PLEDs.In WO 04/037887, describe the production method of PLEDs in detail as conventional process, it should change accordingly for individual cases.As mentioned above, polymer of the present invention especially is particularly suitable as by the PLEDs of this method production or the electroluminescent material of display.
For purpose of the present invention, electroluminescent material thinks that be meant can be as the material of the active layer of PLED.Active layer be meant can be luminous when applying electric field layer (luminescent layer), and/or it just can improve and/or the injection of negative electrical charge and/or transmission (electric charge injects or charge transport layer).Also can between luminescent layer and hole injection layer, be used as " resilient coating ".
Therefore the present invention relates to polymer of the present invention or blend equally in PLED, particularly as the purposes of luminescent material.
The invention further relates to the PLED with one or more active layers, wherein one of these active layers comprise one or more polymer of the present invention or blend at least.Described active layer for example can be luminescent layer and/or transport layer and/or electric charge injection layer.
With respect to not comprising general formula (1) unit, and herein as poly-spiral shell two fluorenes of quoting of in WO 03/020790, describing near prior art, the poly-fluorenes of in WO 02/077060, describing, with the poly-dihydro phenanthrene of describing in WO 05/014689, polymer of the present invention has following beyond thought advantage:
Than the longer life-span of polymer comparable, that other composition is identical, described comparable polymer does not comprise the unit of general formula (1), and contains two (three arylamine) derivatives that its fragrance unit, center does not have planar structure for it.The increase in life-span is very important for using, because particularly under the situation of look and glow green polymer of turning blue, and the biggest obstacle that is to use of the deficiency in life-span so far.
Polymer of the present invention has comparable or higher luminous efficiency in application under the situation of other same composition.This is very important, thereby because can obtain identical lightness with lower energy consumption, this is very important, particularly at the movable application (portable phone that relies on rechargeable battery, beeper, the display of personal digital assistant etc.) in or can obtain other application.On the contrary, identical energy consumption can obtain higher lightness, and this for example uses for illumination is interesting.
If use the three arylamine unit of (and the be preferably rigidity) bridge-jointing unit with plane, then the current/voltage curve is precipitous.Therefore, three arylamine unit of the present invention are the better hole conductor in three arylamine unit than prior art.
Application this paper of the present invention and following embodiment relate to the purposes of polymer of the present invention in PLEDs and corresponding display.Although being subjected to specification limits, for those of ordinary skills, do not need other performing creative labour, just polymer of the present invention can be used for semiconductor (perhaps, under suitable doping situation, also be used for conductor), and be further used in other the electronic device, organic field effect tube (O-FETs) for example, organic integration circuit (O-ICs), OTFT (O-TFTs), organic solar batteries (O-SCs), organic field quenching device (O-FQDs) or also have organic laser diode (O-1asers) is only mentioned several application.The present invention relates to the purposes of polymer of the present invention in corresponding device equally.Therefore the invention still further relates to the organic field effect tube (O-FETs) that comprises a kind of polymer of the present invention at least, organic integration circuit (O-ICs), OTFT (O-TFTs), organic solar batteries (O-SCs), organic field quenching device (O-FQDs) and organic laser diode (O-lasers).
In addition for those of ordinary skills, under the situation that does not need other creative works, the above-mentioned description for conjugation or partly conjugated polymer that provides easily can be applied to conjugation or partly conjugated dendritic or oligomer.Therefore the invention still further relates to the dendritic and the oligomer of this class.
Embodiment:
Embodiment 1:N, N '-two (4-bromophenyl)-N, N '-two (4-tert-butyl-phenyl)-9,9-dioctyl fluorene-2, synthetic (the monomer EM 1 of the present invention) of 7-diamines
Figure A20058001320300231
A) N, N '-xenyl-N, N '-two (4-tert-butyl-phenyl)-9,9-dioctyl fluorene-2,7-diamines
With 2 of 26g (47.4mmol), 7-two bromo-9, the 9-dioctyl fluorene is (as M.Ranger, M.Leclerc, Chem.Commun.1997 describes synthetic described in 1597), and the 4-tert-butyl-phenyl phenyl amine of 20.2g (91mmol) is (as J.Org.Chem.2003, synthesize described in 68,452) de gassed solution N in 150ml toluene 2Saturated 1 hour.Then at first with the P of 174mg (0.86mmol) ( tBu) 3, then with the Pd (OAc) of 96mg (0.42mmol) 2Join in the described solution; The solid state N aO that adds 5.4g (56mmol) subsequently tBu.With described reaction mixture refluxed 5 hours.Behind the cool to room temperature, carefully add the NaCN of 0.8g and the water of 40ml.H with 4 * 50ml 2O washs organic facies, and uses dried over mgso, removal of solvent under reduced pressure.Carry out chromatogram purification with silica gel and obtain yellow oil.According to high pressure lipuid chromatography (HPLC) purity is that 99.3% productive rate is 33g (theoretical value 85%).
1H-NMR(CDCl 3，500MHz)：0.65(m，4H)，0.83(t，J＝7.03Hz，6H)，0.99-1.28(m，20H)，1.31(s，18H)，1，71-1.79(m，4H)，6.90-7.11(m，12H)，7.21-7.31(m，10H)，7.40-7.51(m，2H).
B) N, N '-two (4-bromophenyl)-N, N '-two (4-tert-butyl-phenyl)-9,9-dioctyl fluorene-2,7-diamines (EM 1)
With the N of 36.6g (43.7mmol), N '-xenyl-N, N '-two (4-tert-butyl-phenyl)-9,9-dioctyl fluorene-2, the 7-diamines is introduced among the THF of 500ml.To be dissolved in the NBS solution of the 15.15g (84.4mmol) among the 300ml THF subsequently, dropwise add, and mixture will be placed into room temperature, and stir 4h in addition 0 ℃ of lucifuge.The water of 500ml joins in the described mixture subsequently, described mixture CH 2Cl 2Extract.Use the dried over mgso organic facies, under reduced pressure remove and desolvate.With the hexane agitator treating product and the suction filtration of heat, obtain the white solid of 35g (theoretical value 68%), repeatedly after the recrystallization, the purity of high pressure lipuid chromatography (HPLC) is 99.9% from ethyl acetate.
1H-NMR(CDCl 3，500MHz)：0.66(m，4H)，0.85(t，J＝7.03Hz，6H)，0.99-1.28(m，20H)，1.33(s，18H)，1，73-1.79(m，4H)，6.85-7.10(m，12H)，7.21-7.35(m，8H)，7.40-7.51(m，2H).
Embodiment 2:N, N '-two (4-bromophenyl)-N, N '-two (4-tert-butyl-phenyl)-9,10-dibutyl-9,10-dimethoxy-9,10-dihydro phenanthrene-2, synthetic (the monomer EM 2 of the present invention) of 7-diamines
A) N, N '-xenyl-N, N '-two (4-tert-butyl-phenyl)-9,10-dibutyl-9,10-dimethoxy-9,10-dihydro phenanthrene-2,7-diamines
Similar embodiment 1a) synthesize, with 2 of 24.2g (47.4mmol), 7-two bromo-9,10-dibutyl-9,10-dimethoxy-9,10-dihydro phenanthrene (as synthesizing that WO 05/014689 describes) is as raw material.Obtain yellow oil with the silica gel chromatograph purifying.High pressure lipuid chromatography (HPLC) purity is that 99.0% productive rate is 30g (theoretical value 81%).
1H-NMR(CDCl 3，500MHz)：0.53(m，2H)，0.81(t，J＝7.03Hz，6H)，0.94-1.19(m，6H)，1.25(s，18H)，1.62(m，2H)，2.05(t，J＝7.03Hz，2H)，3.31(s，6H)，6.61-7.5(m，24H).
B) N, N '-two (4-bromophenyl)-N, N '-two (4-tert-butyl-phenyl)-9,10-dibutyl-9,10-dimethoxy-9,10-dihydro phenanthrene-2,7-diamines (EM 2)
Similar embodiment 1b) synthesize, the N of 34.9g (43.7mmol), N '-xenyl-N, N '-two (4-tert-butyl-phenyl)-9,10-dibutyl-9,10-dimethoxy-9,10-dihydro phenanthrene-2, the 7-diamines is as raw material.From ethyl acetate repeatedly after the recrystallization, obtain high pressure lipuid chromatography (HPLC) purity and be 99.9% white solid 24g (theoretical value 70%).
1H-NMR(CDCl 3，500MHz)：0.53(m，2H)，0.81(t，J＝7.03Hz，6H)，0.94-1.19(m，6H)，1.25(s，18H)，1.62(m，2H)，2.05(t，J＝7.03Hz，2H)，3.31(s，6H)，6.85-7.05(m，10H)，7.11-7.20(m，2H)，7.25-7.33(m，8H)，7.42-7.48(m，2H)
Embodiment 3:N, N '-two (4-bromophenyl)-N, N '-two (4-tert-butyl-phenyl)-2 ', 7 '-two (tert-butyl group)-9,9 '-spiral shell two fluorenes-2, synthetic (the monomer EM 3 of the present invention) of 7-diamines
A) N, N '-xenyl-N, N '-two (4-tert-butyl-phenyl)-2 ', 7 '-two (tert-butyl group)-9,9 '-spiral shell two fluorenes-2, the 7-diamines
Similar embodiment 1a) synthesize, 2 of 31.0g (54mmol), 7-two bromo-2 ', 7 '-two (tert-butyl group)-9,9 '-spiral shell two fluorenes are as raw material.Obtain yellow oil with the silica gel chromatograph purifying.The productive rate of high pressure lipuid chromatography (HPLC) purity 99.2% is 50g (theoretical value 99%).
1H-NMR(acetone-d 6，500MHz)：1.28(s，36H)，6.39(s，2H)，6.81-6.89(m，12H)，6.98(dd，J＝2Hz，J＝8.3Hz，2H)，7.05-7.20(m，12H)，7.34(dd，J＝1.7Hz，J＝8.0Hz，2H)，7.06(d，J＝8.0Hz，2H)，7.79(d，J＝8.3Hz，2H).
B) N, N '-two (4-bromophenyl)-N, N '-two (4-tert-butyl-phenyl)-2 ', 7 '-two (tert-butyl group)-9,9 '-spiral shell two fluorenes-2,7-diamines (EM 3)
Similar embodiment 1b) synthesize, the N of 52g (60.8mmol), N '-xenyl-N, N '-two (4-tert-butyl-phenyl)-2 ', 7 '-two (tert-butyl group)-9,9 '-spiral shell two fluorenes-2, the 7-diamines is as raw material.From ethyl acetate repeatedly after the recrystallization, obtain high pressure lipuid chromatography (HPLC) purity and be 99.8% white solid 68g (theoretical value 97.5%).
1H-NMR(CDCl 3，500MHz)：1.25(s，36H)，6.49(s，2H)，6.65-7.15(m，20H)，7.32(dd，J＝1.6Hz，J＝8.0Hz，2H)，7.56(d，J＝8.0Hz，2H)，7.66(s，J＝8.0Hz，2H).
Embodiment 4: synthetic other comonomers
The structure of other monomers (M) that is used for polymer of the present invention and comparative polymer is as follows.Monomer M 1-M6 synthesizes at WO 03/020790, describes in WO 05/014689 and the list of references wherein quoted.
Figure A20058001320300261
Embodiment 5: polymer synthetic
As described in WO 03/048225, by SUZUKI coupling synthetic polymer.The composition of synthetic polymer P 1-P5 sees Table 1.In addition, synthetic comparative polymer C1-C5, it comprises monomer M 4 rather than monomer EM 1 of the present invention and EM 2.The composition of comparative polymer sees Table 1 equally.
The production of embodiment 6:PLEDs
The purposes of research polymer in PLEDs.Described PLEDs is two coating systems under each situation, i.e. base material ∥ ITO ∥ PEDOT ∥ polymer ∥ negative electrode.PEDOT is that (Baytron P is from H.C.Stark, Goslar) for polythiofuran derivative.The negative electrode of Shi Yonging is Ba/Ag (Aldrich) in all cases.The method of producing PLEDs be described in detail in WO 04/037887 and the list of references wherein quoted in.
Embodiment 7-11: device embodiment
That uses polymer P 1-P5 acquisition in PLEDs the results are shown in Table 1.Provide the electroluminescence result who uses comparative polymer C1-C5 to obtain equally.Because the glow color of polymer of the present invention and comparative polymer is always not identical, for obtaining better comparability, therefore initial lightness is 400cd/m 2Corrected value and y color coordinate 0.2 be used for representing turning blue life-span of coloured light polymer.
It is evident that, comprise the polymer of the present invention of the three arylamine unit, plane of general formula of the present invention (1), have obviously better electroluminescent properties, particularly life-span than the polymer of the three arylamine unit that comprise prior art.Therefore, observing the life-span is increased to up to greater than 6 times (polymer P 2 or C2).This influence is not for all polymer all so significantly, but all observes significant life-span increase for all polymer of the present invention.
Embodiment Polymer Amine Other monomers Maximal efficiency/cd/A 100cd/m 2Under U/V CIEx/y a The life-span of proofreading and correct b/h
77 (contrasts) 88 (contrast), 99 (contrasts) 10 10 (contrast) 11 11 (contrast) P1 C1 P2 C2 P3 C3 P4 C4 P5 C5 10％EM1 10％M4 10％EM1 10％M4 10％EM1 10％M4 10％EM1 10％M4 10％EM1 10％M4 50％M1，40％M2 50％M1，40％M2 50％M1，40％M3 50％M1，40％M3 50％M1，30％M2，10％M7 50％M1，30％M2，10％M7 50％M1，30％M3，10％M5 50％M1，30％M3，10％M5 50％M1，20％M3，20％M6 50％M1，20％M3，20％M6 3.95 2.86 3.78 2.97 3.70 2.97 4.36 4.38 9.24 8.29 4.9 4.4 4.1 5.7 4.8 4.5 4.3 3.8 3.4 3.1 0.16/0.23 0.16/0.18 0.17/0.24 0.15/0.15 0.17/0.24 0.16/0.21 0.21/0.36 0.19/0.31 0.32/0.57 0.33/0.58 53 24 105 17 55 12 102 80 883 384
Table 1: the device result who uses polymer of the present invention and comparative polymer
aCIE coordinate: the color coordinate of the Commission Internationale de 1 ' Eclairage 1931.
bLife-span: 50% the time that drops to initial lightness up to lightness.The correction life-span relates to 6.6w/m 2Energy density, i.e. 400cd/m when yCIE color coordinate 0.2 2Lightness.The described correction life-span can be from initial lightness, and the life-span of color coordinate and practical measurement calculates.
Embodiment 12: the contrast of current/voltage curve
Current density/voltage curve of polymer P 2 and comparative polymer C2 is seen Fig. 1.It is evident that, comprise the polymer P 2 of three arylamine unit of the present invention, than the comparative polymer C2 of the three arylamine unit that comprise prior art, characteristic curve is obviously more precipitous.Therefore, apparent three arylamine unit of the present invention are better hole conductor.

Claims (26)

1. one kind comprises at least the conjugation of the general formula of 0.1mol% (1) unit or partly conjugated polymer,
Figure A2005800132030002C1
General formula (1)
Use therein described symbol and mark have following implication:
A is in occurring each time, and is identical or different, is N, P or As
X is in occurring each time, and identical or different is, has the divalence planar conjugate system of 6-40 carbon atom, and it comprises 2 arlydene at least, and it can be by R 1Replace;
Ar 1, Ar 2, Ar 3, Ar 4, Ar 5In occurring each time, identical or different is, has the fragrance or the heteroaromatic ring system of 2-40 carbon atom, can be by one or more radicals R 1Replace, condition is if this group does not have the straight key that combines with polymer chain, group Ar 1-Ar 5Do not represent the condensed ring system;
R 1In occurring each time, identical or different is H, F, Cl, Br, I, CN, NO 2, OH, N (R 1) 2, Si (R 2) 3, B (R 2) 2, have the straight chain of 1-40 carbon atom, side chain or cycloalkyl, alkoxyl or thio alkoxy, wherein, in addition, one or more non-adjacent carbon atoms can be by-CR 2=CR 2-,-C ≡ C-,-NR 2-,-O-,-S-,-CO-O-or-O-CO-O-replaces, wherein, in addition, one or more H atoms can be replaced by fluorine, have the aryl of 2-40 carbon atom, heteroaryl, aryloxy group or heteroaryloxy, wherein, in addition, one or more carbon atoms can be by O, S or N replace, and they in addition can be by one or more non-aryl R 1Replace; Two or more herein R 1Group also can form aliphatic series or fragrance each other, list or polycyclic system;
R 2In occurring each time, identical or different, be H or aliphatic series or aromatic hydrocarbon group with 1-20 carbon atom;
N is in occurring each time, and is identical or different, is 0,1 or 2;
The unit and the polymer of general formula (1) pass through Ar 1-Ar 5One or two connections of group;
Except the polymer of general formula (2),
Figure A2005800132030003C1
General formula (2)
Wherein: Ar 21, Ar 22, Ar 24Each arlydene naturally, it can the carrier band substituting group; Ar 25Be arlydene or many fused rings of divalence group, it can the carrier band substituting group; Ar 23And Ar 26Each alkyl naturally, aralkyl, perhaps aryl, it can the carrier band substituting group; m 1Be 0,1,2 or 3; n 1It is natural number.
2. according to the polymer of claim 1, it is characterized in that they are conjugated polymers.
3. according to the polymer of claim 1 and/or 2, it is characterized in that dihedral angle between at least two the arylene group of unit X is less than 30 °.
4. according to one or the multinomial polymer of claim 1-3, it is characterized in that unit X is the conjugated system of rigid plane, do not depart from flatness around the singly-bound rotation.
5. according to one or the multinomial polymer of claim 1-4, it is characterized in that general formula (1) unit is by unit Ar 1-Ar 5Bonding enters polymer like this, and it makes even carbon atom or corresponding O, and N and/or S are connecting between polymer and described nitrogen or phosphorus or the arsenic atom A.
6. according to one or the multinomial polymer of claim 1-5, the unit that it is characterized in that general formula (1) is in conjunction with the main chain that enters described polymer.
7. according to the polymer of claim 6, the unit that it is characterized in that general formula (1) is by group Ar 1And Ar 3Be attached on the polymer.
8. according to or the multinomial polymer of claim 1-7, it is characterized in that, other construction unit is selected from following unit: the unit that forms polymer backbone, modify the unit of form or glow color, improve the unit of hole injection and/or hole transport characteristic, improve that electronics injects and/or the unit of electron transport performance, have the unit of the combination of last-mentioned two kinds of unit, from the luminous unit of triplet state and/or improve the unit of the transition from the singlet to the triplet state.
9. polymer according to Claim 8 is characterized in that they comprise the unit of the described polymer backbone of formation of 50mol% at least.
10. according to one or the multinomial polymer of claim 1-9, it is characterized in that the ratio of general formula (1) unit is 1-50mol%.
11., it is characterized in that the ratio of general formula (1) unit is 5-30mol% according to the polymer of claim 10.
12. one or multinomial polymer according to claim 1-11 is characterized in that described symbol A, and be identical or different, represents N or P in occurring each time.
13. one or multinomial polymer according to claim 1-12 is characterized in that described symbol X, and be identical or different, represents the group of general formula (3) in occurring each time:
Figure A2005800132030004C1
General formula (3)
The wherein following sign flag of using that is suitable for:
Y is in occurring each time, and is identical or different, is-C (R 1) 2-,-C (R 1) 2-C (R 1) 2-,-N (R 1)-,-O-,-S-,-P (R 1)-,-P (=O) (R 1)-,-O-C (R 1) 2-or-O-C (=O)-;
M is in occurring each time, and is identical or different, is 0 or 1, and wherein under the situation of symbol m=O, group Y omits and do not correspond to chemical bond;
O, p is in occurring each time, and is identical or different, is 0 or 1, and condition is that o and p can not be 0 simultaneously, and wherein under one of mark o or p were 0 situation, group Y was omitted and does not correspond to chemical bond;
Q is in occurring each time, and is identical or different, is 0,1 or 2;
Dotted line key in the general formula (3) is represented being connected of atom A in the construction unit of this construction unit and general formula (1) herein.
14. one or multinomial polymer according to claim 1-13 is characterized in that described symbol Ar 1-Ar 5, identical or different, in occurring each time representative have 4-30 carbon atom, can be by R 1The fragrance or the heteroaromatic ring system that replace.
15. one or multinomial polymer according to claim 1-14 is characterized in that described symbol n, and be identical or different, represents 0 or 1 in occurring each time.
16., it is characterized in that the unit of general formula (1) has symmetrical structure according to or the multinomial polymer of claim 1-15.
17. according to or the multinomial polymer of claim 1-16, what the unit that it is characterized in that general formula (1) was selected from embodiment can be by R 1Structure (1)-(30) that replace.
18. according to or the multinomial polymer of claim 1-17, it is characterized in that they pass through SUZUKI, YAMAMOTO, STILLE or HARTWIG-BUCHWALD polymerization preparation.
19. one of claim 1-18 or multinomial one or more polymer and other polymerizations, oligomeric, blend dendrite or low molecular weight compound.
20. one or multinomial one or more polymer or solution and the preparation of blend in one or more solvents of claim 1-19.
21. the dual functional monomeric compound of general formula (4) and general formula (5),
Figure A2005800132030006C1
General formula 4) general formula 5)
A wherein, X, Ar 1, Ar 2, Ar 3, Ar 4, Ar 5, R1, R 2Have the identical implication of describing as claim 1 with n, and and:
Z is in occurring each time, and is identical or different, but is the functional group of copolymerization under C-C or C-N bonding reaction condition.
R is 0 or 1.
22. according to the dual functional monomeric compound of claim 21, it is characterized in that Z is selected from Cl, Br, I, O-tosylate, O-trifluoromethayl sulfonic acid ester, O-SO 2R 1, B (OR 1) 2And Sn (R 1) 3, R wherein 1Has the identical implication of describing as claim 1.
23. the dual functional monomeric compound of claim 21 and/or 22 is characterized in that described C-C bonding reaction is selected from the SUZUKI coupling, YAMAMOTO coupling and STILLE coupling, and described C-N bonding reaction is the HARTWIG-BUCHWALD coupling.
24. one or multinomial polymer and/or blend and/or the purposes of solution in electronic component of claim 1-20.
25. comprise one or more layers electronic component, at least one that it is characterized in that these layers comprises one or multinomial at least a polymer or the blend of claim 1-19.
26. the electronic component of claim 25, it is characterized in that it is polymer organic LED (PLED), organic field effect tube (O-FET), organic integration circuit (O-IC), OTFT (O-TFT), organic solar batteries (O-SC), organic field quenching device (O-FQD) or organic laser diode (O-laser).
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